Method for the Preparation of a Heterophasic Copolymer and uses thereof

ABSTRACT

Methods for preparing an impact copolymer by selecting a continuous phase polymer having a first melt flow rate and selecting a rubber phase polymeric material such that the final melt flow rate of the impact copolymer is within 2 g/10 min of the first melt flow rate. Impact copolymers made from such methods and films and molded articles produced from such impact copolymers are also included.

FIELD

Embodiments of the present invention generally relate to heterophasiccopolymers (also referred to as impact copolymers) for use in end useapplications, including films and molded articles.

BACKGROUND

It has been observed that impact copolymers provide materials that haveparticular physical properties, such as good impact strength andimproved toughness.

However, the high haze of impact copolymers limits the applications forwhich these materials can be utilized. Impact copolymers also have atendency to stress whiten.

Therefore, a need exists to develop an impact copolymer having improvedoptical properties, such as lower haze and decreased stress whitening,while maintaining the physical properties of the impact copolymer.

SUMMARY

Embodiments of the present invention include methods for preparing animpact copolymer having increased clarity. One embodiment of the methodsgenerally includes preparing an impact copolymer by selecting acontinuous phase polymer having a first melt flow rate; and selecting arubber phase polymeric material such that the final melt flow rate ofthe impact copolymer is within 2 g/10 min of said first melt flow rate.

Another embodiment includes an impact copolymer prepared by the methodsdescribed. Yet another embodiment includes films and molded articlesproduced from the impact copolymer prepared by the methods described.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 presents the Atomic Force Microscopy (AFM) Image of 7C92.

FIG. 2 presents the AFM Image of 7C93.

FIG. 3 presents the AFM Image of 7C94.

FIG. 4 presents the AFM Image of 7C95.

FIG. 5 presents the AFM Image of 7C97.

FIG. 6 presents the AFM Image of 7C99.

FIG. 7 illustrates the optical testing results of injection molded stepchips.

DETAILED DESCRIPTION Introduction and Definitions

A detailed description will now be provided. Each of the appended claimsdefines a separate invention, which for infringement purposes isrecognized as including equivalents to the various elements orlimitations specified in the claims. Depending on the context, allreferences below to the “invention” may in some cases refer to certainspecific embodiments only. In other cases it will be recognized thatreferences to the “invention” will refer to subject matter recited inone or more, but not necessarily all, of the claims. Each of theinventions will now be described in greater detail below, includingspecific embodiments, versions and examples, but the inventions are notlimited to these embodiments, versions or examples, which are includedto enable a person having ordinary skill in the art to make and use theinventions when the information in this patent is combined withavailable information and technology.

Various terms as used herein are shown below. To the extent a term usedin a claim is not defined below, it should be given the broadestdefinition persons in the pertinent art have given that term asreflected in printed publications and issued patents. Further, unlessotherwise specified, all compounds described herein may be substitutedor unsubstituted and the listing of compounds includes derivativesthereof.

Embodiments of the invention generally include heterophasic polymers andprocess of forming the same. As used herein, the term “heterophasic”generally refers to a polymer having two or more phases. For example,the first phase may include a homopolymer, such as polypropylene, or acopolymer, such as a random copolymer formed from propylene andethylene. Such first phase is also referred to herein as a continuousphase polymer. Unless otherwise specified, the term propylenehomopolymers include those polymers composed primarily of propylene andlimited amounts of other comonomers, such as ethylene, wherein thecomonomer make up less than about 2 wt. % (e.g., mini randomcopolymers), or less than about 0.5 wt. % or less than about 0.1 wt. %by weight of polymer.

The second phase generally includes a rubber phase, such asethylene-propylene rubber. Such second phase is also referred to hereinas a rubber phase polymeric material. The incorporation of the rer phaseinto the polymer matrix generally improves impact properties. As aresult, the heterophasic polymers may also be referred to as impactcopolymers.

As used herein, “bimodal” refers to a resin and polymerization processfor producing a resin having a distinct low molecular weight portion anda distinct high molecular weight portion.

Catalyst Systems

Catalyst systems useful for polymerizing olefin monomers include anycatalyst system known to one skilled in the art. For example, thecatalyst system may include metallocene catalyst systems, single sitecatalyst systems, Ziegler-Natta catalyst systems or combinationsthereof, for example. As is known in the art, the catalysts may beactivated for subsequent polymerization and may or may not be associatedwith a support material. A brief discussion of such catalyst systems isincluded below, but is in no way intended to limit the scope of theinvention to such catalysts.

For example, Ziegler-Natta catalyst systems are generally formed fromthe combination of a metal component (e.g., a catalyst) with one or moreadditional components, such as a catalyst support, a cocatalyst and/orone or more electron donors, for example.

Metallocene catalysts may be characterized generally as coordinationcompounds incorporating one or more cyclopentadienyl (Cp) groups (whichmay be substituted or unsubstituted, each substitution being the same ordifferent) coordinated with a transition metal through it bonding. Thesubstituent groups on Cp may be linear, branched or cyclic hydrocarbylradicals, for example. The cyclic hydrocarbyl radicals may further formother contiguous ring structures, including indenyl, azulenyl andfluorenyl groups, for example. These contiguous ring structures may alsobe substituted or unsubstituted by hydrocarbyl radicals, such as C₁ toC₂₀ hydrocarbyl radicals, for example.

Polymerization Processes

As indicated elsewhere herein, catalyst systems are used to formpolyolefin compositions. Once the catalyst system is prepared, asdescribed above and/or as known to one skilled in the art, a variety ofprocesses may be carried out using that composition. The equipment,process conditions, reactants, additives and other materials used inpolymerization processes will vary in a given process, depending on thedesired composition and properties of the polymer being formed. Suchprocesses may include solution phase, gas phase, slurry phase, bulkphase, high pressure processes or combinations thereof, for example.(See, U.S. Pat. No. 5,525,678; U.S. Pat. No. 6,420,580; U.S. Pat. No.6,380,328; U.S. Pat. No. 6,359,072; U.S. Pat. No. 6,346,586; U.S. Pat.No. 6,340,730; U.S. Pat. No. 6,339,134; U.S. Pat. No. 6,300,436; U.S.Pat. No. 6,274,684; U.S. Pat. No. 6,271,323; U.S. Pat. No. 6,248,845;U.S. Pat. No. 6,245,868; U.S. Pat. No. 6,245,705; U.S. Pat. No.6,242,545; U.S. Pat. No. 6,211,105; U.S. Pat. No. 6,207,606; U.S. Pat.No. 6,180,735 and U.S. Pat. No. 6,147,173, which are incorporated byreference herein.)

In certain embodiments, the processes described above generally includepolymerizing one or more olefin monomers to form polymers. The olefinmonomers may include C₂ to C₃₀ olefin monomers, or C₂ to C₁₂ olefinmonomers (e.g., ethylene, propylene, butene, pentene, methylpentene,hexene, octene and decene), for example. The monomers may includeethylenically unsaturated monomers, C₄ to C₁₈ diolefins, conjugated ornonconjugated dienes, polyenes, vinyl monomers and cyclic olefins, forexample. Non-limiting examples of other monomers may include norbornene,nobornadiene, isobutylene, isoprene, vinylbenzocyclobutane, sytrene,alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene andcyclopentene, for example. The formed polymer may include homopolymers,copolymers or terpolymers, for example.

Examples of solution processes are described in U.S. Pat. No. 4,271,060,U.S. Pat. No. 5,001,205, U.S. Pat. No. 5,236,998 and U.S. Pat. No.5,589,555, which are incorporated by reference herein.

One example of a gas phase polymerization process includes a continuouscycle system, wherein a cycling gas stream (otherwise known as a recyclestream or fluidizing medium) is heated in a reactor by heat ofpolymerization. The heat is removed from the cycling gas stream inanother part of the cycle by a cooling system external to the reactor.The cycling gas stream containing one or more monomers may becontinuously cycled through a fluidized bed in the presence of acatalyst under reactive conditions. The cycling gas stream is generallywithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product may be withdrawn from the reactor andfresh monomer may be added to replace the polymerized monomer. Thereactor pressure in a gas phase process may vary from about 100 psig toabout 500 psig, or from about 200 psig to about 400 psig or from about250 psig to about 350 psig, for example. The reactor temperature in agas phase process may vary from about 30° C. to about 120° C., or fromabout 60° C. to about 115° C., or from about 70° C. to about 110° C. orfrom about 70° C. to about 95° C., for example, (See, for example, U.S.Pat. No. 4,543,399; U.S. Pat. No. 4,588,790; U.S. Pat. No. 5,028,670;U.S. Pat. No. 5,317,036; U.S. Pat. No. 5,352,749; U.S. Pat. No.5,405,922; U.S. Pat. No. 5,436,304; U.S. Pat. No. 5,456,471; U.S. Pat.No. 5,462,999; U.S. Pat. No. 5,616,661; U.S. Pat. No. 5,627,242; U.S.Pat. No. 5,665,818; U.S. Pat. No. 5,677,375 and U.S. Pat. No. 5,668,228,which are incorporated by reference herein.)

Slurry phase processes generally include forming a suspension of solid,particulate polymer in a liquid polymerization medium, to which monomersand optionally hydrogen, along with catalyst, are added. The suspension(which may include diluents) may be intermittently or continuouslyremoved from the reactor where the volatile components can be separatedfrom the polymer and recycled, optionally after a distillation, to thereactor. The liquefied diluent employed in the polymerization medium mayinclude a C₃ to C₇ alkane (e.g., hexane or isobutane), for example. Themedium employed is generally liquid under the conditions ofpolymerization and relatively inert. A bulk phase process is similar tothat of a shiny process with the exception that the liquid medium isalso the reactant (e.g., monomer) in a bulk phase process. However, aprocess may be a bulk process, a slurry process or a bulk slurryprocess, for example.

In a specific embodiment, a slurry process or a bulk process may becarried out continuously in one or more loop reactors. The catalyst, asslurry or as a dry free flowing powder, may be injected regularly to thereactor loop, which can itself be filled with circulating slurry ofgrowing polymer particles in a diluent, for example. Optionally,hydrogen may be added to the process, such as for molecular weightcontrol of the resultant polymer. The loop reactor may be maintained ata pressure of from about 27 bar to about 50 bar or from about 35 bar toabout 45 bar and a temperature of from about 38° C. to about 121° C.,for example. Reaction heat may be removed through the loop wall via anymethod known to one skilled in the art, such as via a double jacketedpipe or heat exchanger, for example. Alternatively, other types ofpolymerization processes may be used, such as stirred reactors inseries, parallel or combinations thereof, for example.

In one or more embodiments, the impact copolymers are formed byincorporating a rubber fraction into the polymer matrix by methods knownto one skilled in the art, such as via mechanical blending orco-polymerization, for example. The co-polymerization process mayinclude at least two stages, wherein the propylene homopolymer isproduced in a first reaction zone, the product of which is transferredto a second reaction zone for contact with a comonomer and additionalpropylene monomer.

Embodiments of the invention generally include contacting the propylenehomopolymer with ethylene and additional propylene monomer to form aresulting polymer having greater than 2 wt. %, or greater than 4 wt. %,or greater than 8 wt. %, or greater than 10 wt. %, or greater than 12 wt%, or greater than 14 wt % ethylene; or from 2 wt. % to 14 wt %, or from4 wt % to 12 wt %, or from 8 wt % to 10 wt % ethylene.

The R ratio, which is the ethylene content of the rubber and isdescribed further below, is the ratio of ethylene to propylene.Increased propylene character is achieved by decreasing the R ratio,which is achieved by modifying the ratio of ethylene to propylene in thesecond reactor of the heterophasic polymer production process. Modifyingthe rubber intrinsic viscosity, further defined below, is achieved byincreasing the hydrogen content, which results in chain termination inthe second reactor.

Polymer Product

Upon removal from the reactor, the polymer may be passed to a polymerrecovery system for further processing, such as addition of additivesand/or extrusion, for example.

In the embodiments described herein, the polymer, which may also bereferred to herein as a heterophasic copolymer, is propylene based. Asused herein, the term “propylene based” refers to a polymer having atleast about 80 wt. %, or at least about 85 wt. % or at least about 90wt. % polypropylene.

In an embodiment, the polypropylene based polymer generally has a meltflow rate of from 0.5 g/10 min. to 20 g/10 min., or from 4 g/10 min. to15 g/10 min., or from 6 g/10 min. to 13 g/10 min., or from 8 g/10 min.to 11 g/10 min.

In an embodiment, the impact copolymer generally has a melt flow rate offrom 0.5 g/10 min. to 10 g/10 min., or from 4 g/10 min. to 8 g/10 min.,or from 5 g/10 min to 7.5 g/10 min.

An impact copolymer, as described above, has a first phase that, in oneembodiment, may include the polypropylene based homopolymer and a secondphase that may include a rubber phase, such as an ethylene-propylenerubber. In one embodiment, the intrinsic viscosity of the rubber phasemay be from 1.0 dl/g to 3.0 dl/g, or from 1.4 dl/g to 2.4 dl/g, or from1.8 dl/g to 2.2 dl/g or from 1.9 dl/g to 2.0 dl/g. In one embodiment,the viscosity of the continuous phase polymer may be from 1.0 dl/g to3.0 dl/g, or from 1.4 dl/g to 2.4 dl/g, or from 1.8 dl/g to 2.2 dl/g orfrom 1.9 dl/g to 2.0 dl/g. In one embodiment, the viscosity of therubber phase may be from 1.0 dl/g to 3.0 dl/g, or from 1.4 dl/g to 2.4dl/g, or from 1.8 dl/g to 2.2 dl/g or from 1.9 dl/g to 2.0 dl/g.

In one embodiment, the ethylene content of the impact copolymer may befrom 5 wt % to 15 wt %, or from 7 wt % to 14 wt %, or from 8 wt % to 12wt %, or from 9 wt % to 11 wt %.

In one embodiment, the R ratio may be from 0.25 to 0.50, or from 0.30 to0.45, or from 0.32 to 0.41.

In one embodiment, the impact copolymer may have a melting point,measured by DSC, from 135° C. to 170° C., or from 140° C. to 165° C., orfrom 145° C. to 160° C.

In one embodiment, the impact copolymer may have a xylene solublefraction of from 15 wt % to 25 wt %, or from 16 wt % to 20 wt %, or from17 wt % to 18.5 wt %.

In one embodiment, the impact copolymer may have an acetone insolublefraction of from 10 wt % to 25 wt %, or from 15 wt % to 20 wt %, or from16 wt % to 17 wt %.

In one embodiment, the impact copolymer may have an Mn of from 25,000 to80,000, or from 35,000 to 75,000, or from 40,000 to 55,000. In oneembodiment, the impact copolymer may have an Mw of from 150,000 to450,000, or from 225,000 to 350,000, or from 275,000 to 325,000. In oneembodiment, the impact copolymer may have an Mz of from 450,000 to1,500,000, or from 600,000 to 1,250,000, or from 700,000 to 1,000,000.

In one embodiment, the ethylene-propylene rubber phase may have a % Etin XSAI (xylene solubles—acetone insolubles), by NMR, of from 30 wt % to50 wt %, or from 35 wt % to 45 wt %, or from 40 wt % to 45 wt %. In oneembodiment, the ethylene-propylene rubber phase may have a % Et inPellet, by NMR, of from 7 wt % to 15 wt %, or from 8 wt % to 12 wt %, orfrom 9 wt % to 11 wt %.

In one embodiment, the first phase of the impact copolymer may be arandom copolymer. Two monomers, such as propylene and a comonomer, maybe introduced into the first reactor to form a random copolymer ratherthan a homopolymer. Typically comonomer levels are between 0.1% and 4%by weight. The preferred comonomer is ethylene.

In one embodiment, additives may also be included in the finalcomposition. Nucleators may include any nucleator known to one skilledin the art. For example, non-limiting examples of nucleators may includecarboxylic acid salts, including sodium benzoate, talc, phosphates,metallic-silicate hydrates, organic derivatives of dibenzylidenesorbitol, sorbitol acetals, organophosphate salts and combinationsthereof. In one embodiment, the nucleators are selected from AmfineNa-11 and Na-21, commercially available from Amfine Chemical, MillikenHPN-68, and Millad 3988, commercially available from Milliken Chemical.

In an embodiment, the nucleators may be used in concentrations of fromabout 0 to about 3000 ppm, or from about 5 ppm to about 1000 ppm or fromabout 10 ppm to about 500 ppm by weight of the polymer, for example.

The additives may contact the polymer by any method known to one skilledin the art, For example, the additives may contact the polymer prior toextrusion (within the polymerization process) or within the extruder,for example. In one embodiment, the additives contact the polymerindependently. In another embodiment, the additives are contacted withone another prior to contacting the polymer. In one embodiment, thecontact includes blending, such as mechanical blending, for example.

Product Application

The polymers and blends thereof are useful in applications known to oneskilled in the art, such as forming operations (e.g., film, sheet, pipeand fiber extrusion and co-extrusion as well as blow molding, injectionmolding and rotary molding). Films include blown or cast films formed byco-extrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, and membranes, for example, in food-contact andnon-food contact application. Fibers include melt spinning, solutionspinning and melt blown fiber operations for use in woven or non-wovenform to make filters, diaper fabrics, medical garments and geotextiles,for example. Extruded articles include medical tubing, wire and cablecoatings, geomembranes and pond liners, for example. Molded articlesinclude single and multi-layered constructions in the form of bottles,tanks, large hollow articles, rigid food containers and toys, forexample.

In particular, the polymers are useful for cast film applications. Inone example of a cast film process, a polymer is extruded out of a flatdie face and cooled rapidly (typically on a chilled roll) to form a filmwith a thickness which can range from 0.4 mil to 15 mil.

Additionally, the polymers are useful for injection molded parts andinjection stretch blow molding (ISBM). In one example of an injectionmolding process, material is mechanically and thermally heated in ascrew and driven into a closed cavity to form a finished part. In oneexample of an ISBM process, hollow parts (known as preforms) are formedin an injection molding process. The parts are subsequently heatedstretched and blown with air to form a hollow part with a thinner wallthickness than the preform.

In one embodiment, the films produced may have haze properties of from5% to 85%, or from 6% to 60%, or from 25% to 55%. In one embodiment, thefilms produced may have gloss at 45° of from 5% to 65%, or from 7.5% to25%, or from 9% to 12%.

In one embodiment, the films produced may have an average particle size,measured using AFM, of from 0.50 μm to 4.0 μm, or from 0.7 μm to 3.5 μm,or from 1.0 to 2.7 μm, or from 1.5 μm to 2.1 μm.

In one embodiment, the films produced may have a 1% secant modulus offrom 55 kpsi to 110 kpsi, or from 70 kpsi to 95 kpsi, or from 80 kpsi to90 kpsi. In one embodiment, the films produced may have tensile strengthat yield of from 2000 psi to 4000 psi, or from 2400 psi to 3000 psi, orfrom 2500 psi to 2800 psi. In one embodiment, the films produced mayhave an elongation at yield of from 7.5% to 15%, or from 8% to 12%, orfrom 9% to 11%.

In one embodiment, the films produced may have a dart drop of from 300 gto greater than 1200 g, or from 300 g to 600 g, or from 400 g to 500 g.In one embodiment, the films produced may have an Elmendorf Tear in themachine direction of from 150 g to 250 g, or from 160 g to 200 g, orfrom 175 g to 190 g. In one embodiment, the films produced may have afilm puncture of from 1.5 in-lbs to 2.5 in-lbs, or from 1.7 in-lbs to2.2. in-lbs, or from 1.8 in-lbs to 2.0 in-lbs.

In one embodiment, the injection molded articles produced may have hazeproperties at a sample thickness of 0.02 inches of from 20% to 95%, orfrom 30% to 80%, or from 40% to 70%. Additional examples of the hazeproperties of injection molded articles at varying thicknesses isillustrated in FIG. 7.

In one embodiment, the injection molded articles produced may have aflexural modulus of from 90 kpsi to 250 kpsi, or from 150 kpsi to 200kpsi, or from 175 kpsi to 190 kpsi. In one embodiment, the injectionmolded articles produced may have a tensile modulus of from 100 kpsi to250 kpsi, or from 150 kpsi to 200 kpsi, or from 170 kpsi to 190 kpsi. Inone embodiment, the injection molded articles produced may have atensile strength at yield of from 2500 psi to 4500 psi, or from 3000 psito 4000 psi, or from 3500 psi to 3800 psi. In one embodiment, theinjection molded articles produced may have a tensile strength at breakof from 1500 psi to 3000 psi, or from 1700 psi to 2500 psi, or from 1800psi to 2300 psi.

In one embodiment, the injection molded articles produced may have anelongation at yield of from 5% to 15%, or from 6% to 11%, or from 7% to9%. In one embodiment, the injection molded articles produced may havean annealed heat distortion of from 150° F. to 200° F., or from 170° F.to 190° F.

In one embodiment, the ISBM article produced may have haze properties offrom 10% to 90%, or from 20% to 80%, or from 50% to 70%. In oneembodiment, the ISBM article produced may have a gloss at 45° of from10% to 65%, or from 15% to 60%, or from 20% to 50%.

In one embodiment, the ISBM article produced may have a bumpercompression with a load at 0.5 in deflection of from 50 N to 110 N, orfrom 75 N to 100 N, or from 90 N to 100 N. In one embodiment, the ISBMarticle produced may have a top load of from 70 N to 140 N, or from 90 Nto 120 N, or from 100 N to 110 N.

EXAMPLES

The following test methods were used in evaluating the polymer andresulting end use products. Haze: ASTM D1003; Gloss: ASTM D-2457-70;Dart Drop: ASTM D1709; Elmendorf Tear: ASTM D-1922-89; Punctureresistance: force per unit area to puncture a 2 mil film with a 3.17 mmdiameter tip at a speed of 20 in/min; Rubber particle size: atomic forcemicroscopy (AFM); Melt flow rate: ASTM D1238; Differential ScanningCalorimetry (DSC): ASTM D3417 performed at a 10° C./min ramp rate;Intrinsic viscosity: measured by ASTM D5225 and calculated by theformula described below; Xylene solubles: ASTM D5492; AcetoneInsolubles: calculated as the weight fraction of xylene solublesprecipitated in acetone.

Six sample materials were prepared having the characteristics describedbelow (Table 2), using a standard Ziegler-Natta catalyst available fromBasell. 7C92 is a 7 MFR ICP targeted for cast film applications. 7C93and 7C94 represent progressively lower rubber intrinsic viscosity (IV).For 7C97, the IV is similar to the control, but the R ratio (ratio ofethylene to propylene) has been adjusted to increase the propylenecharacter of the IV rubber. 7C95 has similar rubber composition as thecontrol but with a bimodal composition of the homopolymer phase.Finally, 7C99 has more propylene content in the ethylene-propylenerubber (EPR) and has a low level of ethylene in the continuous phase, at4 wt %. The presence of a random copolymer continuous phase makes thismaterial a random heterophasic copolymer (RaHeCo).

Samples were prepared according to the parameters described above.Pellets were tested to verify the composition of the experimentalresins. The results appear in Table 1 below. The samples have reasonablysimilar MFR for testing purposes. With respect to the R ratio, NMR dataon the xylene soluble/acetone insoluble (XSAI) portion of the sampleshows reasonable correlation to the R ratio targeted. Rubber content,based on the percent of XSAI, varied slightly in the samples rangingfrom approximately 15% to 17% for most of the samples. The exception is7C99 sample which showed a much higher XSAI (20%) than the othermaterials. The calculated intrinsic viscosity of the rubber ascalculated from GPC of the XSAI fraction shows a similar trend to thetargeted rubber IV. The calculated intrinsic viscosity was calculatedusing the following formula, [η]=−0.1436+0.0015(Mw)^(0.595), where [η]is the intrinsic viscosity and Mw is the weight average molecularweight. Those of ordinary skill in the art understand that, for a linearpolymer, there is a direct relationship between log [η] and log [Mw].

TABLE 1 Measured versus reported properties of pellet samples 7C92 7C937C94 7C95 7C97 7C99 Test Value Unit Control Low IV Lowest IV Bimodal LowR RaHeCo Reported MFR g/10 min 7.2 6.8 6.0 5.8 7.9 7.3 IV Rubber dl/g2.6 1.8 1.4 2.4 2.2 2 C2 content % 10.3 10.9 8.1 12 7.8 9.4 R ratio(target) 0.41 0.41 0.41 0.41 0.32 0.32 MFR MFR g/10 min 7.6 7.3 6.7 6.37.7 6.6 DSC Tm ° C. 164.1 163.3 164.7 162.7 163.6 144.4 ExtractionXylene % 16.1 17.2 16.9 18.3 18.1 21.2 Solubles Acetone Insol % 14.916.3 15.1 16.9 16.9 20.1 NMR %E in XSAI wt % 41.6 43.4 41.9 43.8 37.732.4 %E in Pellet wt % 9.9 10.4 9.4 11.5 8.8 10.2 GPC Mn g/mol 65,00049,000 37,000 71,000 52,000 28,000 (for XSAI) Mw g/mol 414,000 238,000169,000 433,000 320,000 277,000 MZ g/mol 1,246,000 655,000 452,0001,300,000 992,000 1,008,000 PDI 6.4 4.8 4.5 6.1 6.1 9.9 Calc IV dl/g 3.12.2 1.8 3.2 2.7 2.4

Samples were used to prepare 2 mil cast films using a mini-sheet linewhich consists of a 1.25 inch Welex extruder and a 3 roll stack. Thefollowing set points were used: Zone 1 400° F., Zone 2—420° F., Zone3—450° F., Die 1—470° F., Die 2—470° F. Die gap was set at 20 mil.Extruder RPM and take up were adjusted to achieve a 20 mil film. Filmsamples were tested for optics and physical properties according tostandard testing procedures. In addition to film samples, injectionmolded parts and ISBM bottles were prepared from some of the materialsas described below.

Results from the 2 mil films are summarized in Table 2. From opticalmeasurements, the haze was most affected by the IV of the rubber withlower IV resulting in significantly lower haze. A smaller effect is seenwith adjusting the R ratio. Interestingly, it is noted that the targetMFR of the continuous phase matches the final MFR in the product for7C94 (Table 7, below), which in turn resulted in the lowest haze. Thissuggests that at the selected IV the rubber has a minimal effect on thefinal viscosity suggesting a viscosity match of the two components.

The use of a bimodal matrix in 7C95 had no apparent impact on the filmoptics. Sample 7C97 shows a slightly lower haze suggesting thatincreasing the propylene content of the EPR does improve optics but theeffect is not as significant as adjusting the rubber IV. Like 7C97, thehaze was slightly lower for 7C99, the random hetrophasic copolymer(RaHeCo) but again the effect was not as significant as adjusting therubber IV.

In order to better understand the origin of the improvement in haze,each sample was evaluated with AFM to assess the relative particle sizeof the EPR. The results demonstrate a relatively good correlation withaverage particle size with larger average particle size resulting inhigher haze. FIGS. 1-6 demonstrate the particle size of the EPR withinthe polymer samples using AFM imaging.

TABLE 2 Optical and AFM measurements of 2 mil films. 7C92 7C93 7C94 7C957C97 7C99 Value Units Control Low IV Lowest IV Bimodal Low R RaHeCoOptics Haze % 74.2 28.5 6.2 80.5 59 51.7 Gloss, 45 % 7.5 20.1 63.4 5.99.6 11.5 AFM Average μm 3.59 1.78 0.79 3.46 2.67 2.05 Particle Size StdDev μm 1.41 0.64 0.29 1.22 0.92 0.73

Film samples were subsequently evaluated for physical properties todetermine the effect of the compositional changes on the resulting film(Table 3). With respect to film stiffness, the secant modulus resultsfor 7C92, 7C93, 7C95, and 7C97 are considered the same within theexperimental error of the test. The 7C94 film does show slightly higherstiffness and the 7C99 shows significantly lower stiffness.

Dart drop and puncture resistance represent important properties forfilm. Typically, the use of impact copolymer is to impart better filmtoughness which is represented by these two test values. The resultsshow parity in dart drop values for 7C92, 7C93, and 7C94. A lower dartdrop value is found for 7C95 and higher values for 7C97 and 7C99. Itmust be noted that the rubber content as measured by XSAI did differ inthe samples and may account for a portion of the differences. However,rubber content differed very little between 7C94 and 7C92 as did dartdrop values, suggesting the smaller EPR particle size in 7C94 did notnegatively impact this film property. For 7C97, it is believed that thehigher dart drop value may be associated with the higher rubber contentof this particular sample, so it is difficult to interpret the impact ofR ratio on the dart response. The result in the bimodal sample, 7C95,suggests that the matrix composition does play a significant role in thedart properties. Dart drop values were exceptionally high for 7C99,possibly due to the random copolymeric nature of the continuous (orfirst) phase.

TABLE 3 Physical properties of 2 mil films. 7C92 7C93 7C94 7C95 7C977C99 Value Units Control Low IV Lowest IV Bimodal Low R RaHeCo AcetoneInsol % 14.9 16.3 15.1 16.9 16.9 20.1 1% Secant Mod kpsi 90 89 105 87 9456 Tens Str @ yield psi 2558 2569 2998 2448 2712 2150 Elongation @ yield% 8.8 9.4 10.3 8 9.7 14.1 Dart Drop g 483 491 497 335.2 573 >1270Elmendorf Tear MD g 158.7 184.3 236.7 164 157.6 193.4 Film PunctureIn-lbs 1.706 2.102 1.92 1.626 2.121 1.788 WVTR g/100 in 2/day 0.63 0.550.54 0.62 0.57 0.68

In order to further evaluate the comparative performance of thematerials, samples were injection molded to form step chips for opticalmeasurements, dogbones for Instron measurements, and discs forinstrumented impact tests. The sample 7C95 was not included insubsequent testing due to unremarkable results in previous tests.However, an additional sample was prepared by incorporating Millad 3988at a loading of 2000 ppm in 7C94 which showed the best opticalperformance. Samples were molded according to ASTM D4101; tensiletesting on dogbones was performed according to ASTM D638 and flexmodulus was performed according to ASTM D790.

Results of haze testing on step chips are shown in FIG. 7. Note thathaze was not tested on thicker steps once the haze level exceeded 90%.As with the film samples the lowest haze was found for 7C94 among theoriginal samples. The incorporation of Millad 3988 resulted in a slightimprovement in haze. Similar to the results on cast films, injectionmolded samples show improvement in optics with progressively lowerrubber IV.

Results of physical testing of the injection molded samples are shown inTable 4. Generally, the physical properties of the materials are similarwith the exceptions of 7C99 and the 7C94 containing Millad. The randomheterophasic copolymer, 7C99, shows a lower modulus, tensile strength,and heat distortion temperature with respect to the other samples. Thesample containing Millad shows higher modulus, tensile strength, andheat distortion temperature. The results suggest that for roomtemperature properties the modification of the material, in terms of Rratio and rubber IV, does not significantly alter the physicalproperties. Thus, the improvement in optics does not come at a high costto physical properties.

TABLE 4 Physical properties of injection molded samples. 7C94 w/ ValueUnits 7C92 7C93 7C94 Millad 7C97 7C99 Flex Mod (Chord 4-8N) kpsi 193 187183 202 178 95 Tensile Modulus kpsi 195 169 191 220 188 114 TensileStrength @ Yield psi 3800 3500 3800 4100 3800 2800 Elongation @ Yield %5.4 6.6 8.6 7.9 6.2 10.4 Tensile Srength @ Break psi 1800 1800 2300 25001600 2600 Annealed heat distortion ° F. 186 183 180 199 184 154

Samples were evaluated at three different temperatures usinginstrumented impact (Table 5). Results were similar for the samples for72° F. and 32° F. In general, the control sample, 7C92, exhibitedslightly better impact properties. There was a loss of toughness in thesamples with lower rubber IV, as indicated by lower Total Energy valuesfor all of the experimental samples but property loss was only around15% for the sample with the best optics, 7C94. However, at −4° F., 7C94shows extremely poor impact properties. The results suggest that whilereduction of rubber IV has a minimal effect on the impact resistance ofthe material at ambient temperatures, below the glass transition of thematerial the impact resistance is compromised.

TABLE 5 Instrumented impact results for molded discs. 7C94 w/ Temp UnitsUnits 7C92 7C93 7C94 Millad 7C97 7C99 72° F. Impact Velocity ft/sec 28.228.3 28.2 28.2 28.1 28.2 Impact Energy ft-lbs 89.7 90.0 89.7 89.5 88.989.5 Maximum Load lbf 544 530 526 553 535 467 Energy to Max Load ft-lbs13.6 13.0 12.9 13.5 13.3 11.7 Energy After Max ft-lbs 13.3 11.1 10.211.0 12.3 10.9 Load Total Energy ft-lbs 26.9 24.1 23.0 24.5 25.6 22.6Ductile/Brittle 0/5 0/5 0/5 0/5 0/5 0/5 Failures 32° F. Impact Velocityft/sec 28.2 28.2 28.2 28.2 28.1 28.1 Impact Energy ft-lbs 89 90 90 89 8989 Maximum Load lbf 665 667 667 686 648 608 Energy to Max Load ft-lbs16.8 15.8 15.8 15.9 15.0 14.3 Energy After Max ft-lbs 12.3 12.5 11.810.3 10.3 12.0 Load Total Energy ft-lbs 29.1 28.3 27.5 26.2 25.3 26.2Ductile/Brittle 1/4 0/5 0/5 1/4 0/5 0/5 Failures −4° F. Impact Velocityft/sec 28.1 28.1 28.1 28.1 28.1 28.1 Impact Energy ft-lbs 89 89 89 89 8989 Maximum Load lbf 839 819 246 118 753 790 Energy to Max Load ft-lbs19.3 17.1 2.6 0.6 15.6 17.1 Energy After Max ft-lbs 9.1 5.9 0.29 0.626.38 5.37 Load Total Energy ft-lbs 28.4 23.0 2.9 1.2 22.0 22.5Ductile/Brittle 1/4 0/5 0/5 0/5 1/4 1/4 Failures

As a final study on these materials, each resin was used to moldpreforms on Netstal injection molder using a 23 g preform mold. Thepreforms were conditioned at room temperature for at least 24 hoursbefore they were stretch-blow-molded into bottles on ADS G62 linearinjection stretch blow molder (ISBM). Preforms were tested for optics,top load strength, bumper compression, and drop test performance (Table6). Top load testing and bumper compression represent compressiontesting of the bottles in vertical and horizontal configurations,respectively. Drop testing is performed on filled bottles conditioned at40° F. and dropped from a height of six feet on the bottoms and sides ofthe bottle.

For optical measurements (taken at the bottle side wall), the resultswith ISBM were consistent with observations in films and injectionmolded parts. The reduction in rubber IV resulted in the mostimprovement in clarity. The sample with a lower R ratio, 7C97 and theRaHeCo sample, 7C99 both showed some improvement in clarity. Bumpercompression and top load testing of the bottles show a small reductionin stiffness for the lower rubber IV samples. In drop test performancetesting, the control, 7C92 actually performed relatively poorly with theother samples performing better. Consequently, the modifications made tothe ICP composition did not appear to negatively impact the drop testperformance of the bottles.

TABLE 6 Properties of ISBM bottles prepared with POPP2 samples. TestValue Units 7C92 7C93 7C94 7C95 7C97 7C99 Optics Haze % 75.1 20.3 10.985.1 64.5 29.1 Gloss 45° % 15.7 53.8 62.1 13.8 21.2 48.1 Bumper Load @0.5 in N 102 97 91 91 98 54 Compression deflection Top Load Maximum N135 109 109 136 116 72 Load Drop Test Vertical Fail/Pass 10/12 0/12 0/121/12 4/12 0/12 (6 ft) Horizontal Fail/Pass  0/12 1/12 0/12 0/12 1/120/12

Samples (2 mil films), using the sample materials, were cast on a smallpilot scale cast line equipped with a 1¼ inch Welex extruder and an 8inch coat hanger die. A two zone die heat of 380° F. was used and thebarrel heats of 350, 360, and 370° F. were used for zones 1, 2 and 3,respectively. A cast roll temperature of 60° F. was used on a three-rollstack. Sample properties are provided in Table 7.

TABLE 7 Description of pilot plant samples used for study. DescriptionMaterial ID Very Bimodal Low R Control Low IV low IV matrix ratio RaHeCo7C92 7C93 7C94 7C95 7C97 7C99 Continuous 13-15 9-11 6-8 1.5-2.0/13-1513-15 13-15 Phase MFR Final MFR 7.2 6.8 6 5.8 7.9 7.3 IV Rubber 2.6 1.81.4 2.4 2.2 2 C2 content 10.3 10.9 8.1 12 7.8 9.4 R ratio (target) 0.410.41 0.41 0.41 0.32 0.32

Collected films were evaluated for haze with a BYK Gardner Hazegard PlusSystem using methodology consistent with ASTM D1003 procedure “A”. Glosswas evaluated a BYK Gardner micro-gloss glossmeter in accordance with amethod based on ASTM D-2457-70. Physical properties were measured on 1inch strips of film cut in the machine direction. Testing was conductedon Instron model 1122. Dart drop and Elmendorf tear testing were testedin accordance with ASTM D1709 and ASTM D1922-89, respectively. Punctureresistance was measured on 2 mil cast films with an Instron using a 3.17mm diameter tip and a run speed of 20 in/min. Results from testingappear in Table 8.

TABLE 8 Physical property results for 2 mil cast films. Description 7C927C93 7C94 7C95 7C97 7C99 Units Haze 74 29 6 81 59 52 % Gloss, 45 8 20 636 10 12 % 1% Secant Mod 90 89 105 87 94 56 kpsi Tens Str @ yield 26002600 3000 2400 2700 2200 psi Elongation @ yield 8.8 9.4 10.3 8 9.7 14.1% Dart Drop 480 490 500 340 570 >1200 g Elmendorf Tear MD 160 180 240160 160 190 g Film Puncture 1.7 2.1 1.9 1.6 2.1 1.8 in-lbs

In order to verify that the result translates into other sample forms,each material was used to injection mold step chips and the haze wasmeasured on each step where applicable. The results appear in Table 9.Injection molding was performed on a Toshiba ISE 170 hydraulic injectionmolder equipped with a step chip mold designed by Axxicon.

TABLE 9 Haze values from molded step chips (reported as %) 7C92 7C937C94 7C95 7C97 7C99 Haze (20 mil) 93.6 73.4 39 N/A 90.2 82.5 Haze (40mil) N/A 96.1 71.9 N/A N/A 98.9 Haze (60 mil) N/A N/A 85.8 N/A N/A N/AHaze (80 mil) N/A N/A 95.7 N/A N/A N/A

The experiments examined the effect of lowering the rubber IV, loweringR ratio, the use of a bimodal continuous phase, and the use of a randomcopolymer continuous phase in an impact copolymer system. Film,injection molded parts, and ISBM bottles showed similar trends in theresin performance. A small improvement in optics occurred by creatingmore chemically similar phases, as demonstrated by the lower R ratio(7C95) and RaHeCo (7C99) samples. However, the most marked improvementin optics is seen with lowering the rubber IV. The greatest improvementwas found when the two phases approximately match in viscosity.Reduction in rubber IV significantly compromised impact resistance at−4° F. However, at ambient and even subambient (32° F. for injectionmolded parts and 40° F. for ISBM bottles) there was not a significantloss in impact strength (instrumented impact and drop testing) formaterials with lower rubber IV. The results suggest that the optics ofan impact copolymer can be significantly improved simply by lowering theIV of the rubber. This does increase the stiffness of the resin andslightly lowers the impact strength but the changes are minor except atextremely low temperature.

A lower MFR heterophasic polymer for blown film was created utilizing asimilar approach as above such that a lower IV was used to improve theclarity of the film. The results are shown in Table 10 below for a 2 milfilm. In this case, the IV of the rubber was lowered from 2.4 dl/g inthe control to 1.9 dl/g and 1.5 dl/g. Samples were used to produce blownfilms of a 2 mil thickness. The haze dropped progressively in sampleswith lower rubber IV again demonstrating the effect of lower rubber IVin improving material clarity.

TABLE 10 Physical Properties of lower MFR polymers. 8C30 8C31 8C36 ValueControl Low IV Lowest IV R ratio 0.4 0.4 0.4 MFR Pellets 0.8 1.11 1.69MFR Homo 0.9 1.3 1.4 % C2 Homo — — — Rubber IV 2.4 1.9 1.5 C2 tot (NIR)10.7 10.5 11.2 Haze (%) 48.1 31.1 22

While various embodiments have been shown and described, modificationsthereof can be made by one skilled in the art without departing from thespirit and teachings of the disclosure. The embodiments described hereinare exemplary only, and are not intended to be limiting. Many variationsand modifications of the embodiments disclosed herein are possible andare within the scope of the disclosure. Where numerical ranges orlimitations are expressly stated, such express ranges or limitationsshould be understood to include iterative ranges or limitations of likemagnitude falling within the expressly stated ranges or limitations(e.g., from about 1 to about 10 includes, 2, 3, 4, etc.; greater than0.10 includes 0.11, 0.12, 0.13, etc.). Use of the term “optionally” withrespect to any element of a claim is intended to mean that the subjectelement is required, or alternatively, is not required. Bothalternatives are intended to be within the scope of the claim. Use ofbroader terms such as comprises, includes, having, etc. should beunderstood to provide support for narrower terms such as consisting of,consisting essentially of, comprised substantially of etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present disclosure. Thus, the claims are a further description andare an addition to the embodiments disclosed herein. The discussion of areference herein is not an admission that it is prior art to the presentdisclosure, especially any reference that may have a publication dateafter the priority date of this application. The disclosures of allpatents, patent applications, and publications cited herein are herebyincorporated by reference, to the extent that they provide exemplary,procedural or other details supplementary to those set forth herein.

1-23. (canceled)
 24. An article comprising: an impact copolymer having a continuous phase polymer and a rubber phase polymeric material incorporated into the continuous phase polymer, wherein the continuous phase polymer is a propylene homopolymer or a propylene random copolymer having a comonomer content ranging from 0.1 to 4 weight percent, wherein the impact copolymer has an Mn ranging from 25,000 to 80,000, an Mw ranging from 150,000 to 450,000, and an Mz ranging from 450,000 to 1,500,000; wherein the article is an injection molded article, an injection stretch blow molded article, or a film.
 25. The article of claim 27, wherein the article is the injection molded article, and wherein a 0.02 inch sample of the injection molded article exhibits a haze of from 20% to 95%.
 26. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits a flexural modulus of from 90 kpsi to 250 kpsi.
 27. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits a tensile modulus of from 100 kpsi to 250 kpsi.
 28. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits a tensile strength at yield of from 2500 psi to 4500 psi.
 29. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits a tensile strength at break of from 1500 psi to 3000 psi.
 30. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits an elongation at yield of from 5% to 15%.
 31. The article of claim 27, wherein the article is the injection molded article, and wherein the injection molded article exhibits an annealed heat distortion of from 150° F. to 200° F.
 32. The article of claim 27, wherein the article is the injection stretch blow molded article, and wherein the injection stretch blow molded article exhibits a haze of from 10% to 90%.
 33. The article of claim 27, wherein the article is the injection stretch blow molded article, and wherein the injection stretch blow molded article exhibits a gloss at 45° of from 10% to 65%.
 34. The article of claim 27, wherein the article is the injection stretch blow molded article, and wherein the injection stretch blow molded article exhibits a bumper compression with a load at 0.5 in deflection of from 50 N to 110 N.
 35. The article of claim 27, wherein the article is the injection stretch blow molded article, and wherein the injection stretch blow molded article exhibits a top load of from 70 N to 140 N.
 36. The article of claim 27, wherein the article is the film, and wherein the film exhibits an average particle size, measured by Atomic Force Microscopy, of from 0.50 μm to 4.0 μm.
 37. The article of claim 27, wherein the article is the film, and wherein the film exhibits a 1% secant modulus of from 55 kpsi to 110 kpsi.
 38. The article of claim 27, wherein the article is the film, and wherein the film exhibits a tensile strength at yield of from 2000 kpsi to 4000 kpsi.
 39. The article of claim 27, wherein the article is the film, and wherein the film exhibits an elongation at yield of from 7.5% to 15%.
 40. The article of claim 27, wherein the article is the film, and wherein the film exhibits a dart drop of from 300 g to greater than 1200 g.
 41. The article of claim 27, wherein the article is the film, and wherein the film exhibits an Elmendorf Tear in the machine direction of from 150 g to 250 g.
 42. The article of claim 27, wherein the article is the film, and wherein the film exhibits a film puncture of from 1.5 in-lbs to 2.5 in-lbs.
 43. A method comprising: selecting a continuous phase polymer, wherein the continuous phase polymer is a propylene homopolymer or a propylene random copolymer having a comonomer content ranging from 0.1 to 4 weight percent; selecting a rubber phase polymeric material; incorporating the rubber phase polymeric material into the continuous phase polymer to form an impact copolymer, wherein the impact copolymer has an Mn ranging from 25,000 to 80,000, an Mw ranging from 150,000 to 450,000, and an Mz ranging from 450,000 to 1,500,000; and preparing an article from the impact copolymer, wherein the article is an injection molded article, an injection stretch blow molded article, or a film. 